The present invention relates to a process for the hydroformylation of ethylenically unsaturated compounds, in which at least one complex or compound of a metal of transition group VIII with at least one bidentate phosphine ligand is used as hydroformylation catalyst and at least one of the reaction steps following the hydroformylation reaction is carried out essentially in the absence of carbon monoxide and hydrogen and in the presence of at least one monodentate phosphine ligand.
Hydroformylation or the oxo process is an important industrial process and is employed for preparing aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can, if desired, be hydrogenated by means of hydrogen to form the corresponding oxo alcohols in the same process. The reaction itself is exothermic and generally proceeds under superatmospheric pressure and at elevated temperatures in the presence of catalysts. Catalysts used are Co, Rh, Ir, Ru, Pd or Pt compounds or complexes which may be modified with N- or P-containing ligands to influence the activity and/or selectivity. The hydroformylation reaction results in formation of mixtures of isomeric aldehydes because of the possible addition of CO onto each of the two carbon atoms of a double bond. In addition, double bond isomerization, i.e. a shift of an internal double bond to a terminal position or vice versa, can occur.
Owing to the substantially greater industrial importance of the xcex1-aldehydes, optimization of the hydroformylation catalysts to achieve a very high hydroformylation activity combined with a very low tendency to form double bonds which are not in the xcex1 position is desired. In addition, there is a need for hydroformylation catalysts which lead to good yields of not only xcex1-aldehydes but in particular n-aldehydes. For this purpose, the catalyst has to catalyze the hydroformylation of terminal olefins as selectively as possible.
The use of phosphorus-containing ligands for stabilizing and/or activating the catalyst metal in rhodium-catalyzed low-pressure hydroformylation is known. Suitable phosphorus-containing ligands are, for example, phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes. The most widely used ligands at present are triarylphosphines such as triphenylphosphine and sulfonated triphenylphosphine since these are sufficiently stable under the reaction conditions. However, these ligands have the disadvantage that, in general, only very high excesses of ligand give satisfactory yields, in particular of linear aldehydes. However, this generally reduces the activity.
In Tetrahedron Letters, volume 34, No. 13, page 2107 ff. (1993), in Tetrahedron Letters, volume 36, No. 1, page 75 ff. (1995) and in Chem. Ber. 124, page 1705 ff. (1991), Haenel et al. describe the synthesis of bis(diphenylphosphino)chelates having anthracene, dibenzofuran, dibenzothiophene and xanthene skeletons. Use of these compounds as catalysts is not described.
In J. Chem. Soc., Dalton Trans., 1998, pp. 2981-2988, W. Goertz et al. describe the use of chelating phosphines and phosphonites having a thioxanthene skeleton for the nickel-catalyzed hydrocyanation of styrene. Use in hydroformylation is not described.
In Organometallics 1999, 18, pages 4765 to 4777, van der Veen et al. describe the use of phosphacyclic diphosphines having a xanthene skeleton as ligands for rhodium-catalyzed hydroformylation. A disadvantage of these catalysts is their very low activity which makes use in industrial processes uneconomical.
WO 95/30680 describes bidentate phosphine ligands in which the phosphorus atoms can be bound to a xanthene skeleton and also describes the use of these ligands in catalysts for hydroformylation. A disadvantage of these catalysts is that they are not suitable for the isomerizing hydroformylation of internal olefins with good xcex1- or n-selectivity.
In Organometallics 1995, 14, p. 3081-3089, M. Kranenburg et al. describe the influence of the angle of bite of bidentate phosphine ligands on the regioselectivity of rhodium-catalyzed hydroformylation. Mixed complexes of monodentate and bidentate phosphine ligands were also prepared.
A disadvantage of bidentate phosphine ligands in general and bidentate phosphines having a xanthene skeleton in particular is that the catalytically active species formed from them under the conditions of the hydroformylation reaction are generally not stable in the absence of synthesis gas (CO/H2). It is generally not possible to convert catalyst species which have been deactivated in the absence of CO/H2 back into an active hydroformylation catalyst. For this reason, continuous industrial hydroformylation processes which use catalysts based on bidentate phosphine ligands and encompass isolation of the hydroformylation products and recirculation of the catalyst can be implemented only with great technical difficulty, if at all. In any case, hydroformylation processes using such catalysts suffer from an economic disadvantage.
U.S. Pat. No. 4,169,861 describes a hydroformylation process for preparing 1-alkanals by hydroformylation of xcex1-olefins using a rhodium complex based on a monodentate ligand and a bidentate ligand as catalyst. trans-1,2-Bis(diphenylphosphinomethyl)cycloalkanes and 1,1xe2x80x2-bis(diphenylphosphino)ferrocenes are described as suitable bidentate ligands. U.S. Pat. No. 4,201,728 makes disclosures similar to those of U.S. Pat. No. 4,169,861. U.S. Pat. No. 4,201,714 relates to a rhodium catalyst as used for hydroformylation according to U.S. Pat. No. 4,201,728. According to the three last-named documents, the use of a catalyst based on a monodentate ligand and a bidentate ligand leads to an improvement in the n/iso product selectivity in the hydroformylation of xcex1-olefins. The use of monodentate phosphine ligands in highly selective hydroformylation catalysts based on bidentate phosphine ligands with the aim of stabilizing these catalysts even in the absence of synthesis gas is not described.
It is an object of the present invention to provide an improved process for the hydroformylation of compounds containing at least one ethylenically unsaturated double bond. The process should make it possible to separate off the desired products and recirculate the catalyst with very little drop in the activity of the catalyst used. The use of complicated measures for stabilizing the hydroformylation catalyst used when the desired products are separated off, possibly work-up of the catalyst before it is returned to the reaction, should preferably be able to be omitted. In particular, it should be possible to do without a synthesis gas atmosphere outside the reaction zone used for the hydroformylation. The hydroformylation of xcex1-olefins should preferably result in a very high proportion of xcex1-aldehydes or xcex1-alcohols. In particular, the process should also have a high selectivity to n-products.
We have found that this object is achieved by a hydroformylation process in which the hydroformylation catalyst used comprises at least one complex or compound of a metal of transition group VIII with at least one bidentate phosphine ligand and at least one of the reaction steps following the hydroformylation reaction is carried out essentially in the absence of carbon monoxide and hydrogen and in the presence of at least one monodentate phosphine ligand. The bidentate phosphine ligand used is preferably a compound in which the two phosphine groups are each bound to a different phenyl ring of a xanthene skeleton.
The present invention accordingly provides a process for the hydroformylation of compounds containing at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a catalyst system comprising at least one metal of transition group VIII and at least one bidentate phosphine ligand, which comprises
(i) reacting the compound(s) containing at least one ethylenically unsaturated double bond in a reaction zone in the presence of carbon monoxide, hydrogen and the catalyst system,
(ii) taking an output from the reaction zone and separating it into a fraction enriched in product and a fraction enriched in catalyst system,
(iii) if desired, subjecting the fraction enriched in catalyst system obtained in step (ii) to work-up and
(iv) returning at least part of the fraction enriched in catalyst system, if desired after work-up, to the reaction zone,
where at least one of these steps (ii) to (iv) is carried out essentially in the absence of carbon monoxide and hydrogen and in the presence of at least one monodentate phosphine ligand.
The bidentate phosphine ligand is preferably selected from among compounds of the formula I 
where
A1 and A2 are each, independently of one another a single bond, O, S, SiRaRb, NRc or CR11R12, where
Ra, Rb, Rc, R11 and R12 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R1, R2, R3 and R4 are each, independently of one another, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, which may each bear one, two or three substituents selected from among alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORd, COOxe2x88x92M+, SO3Rd, SOxe2x88x923M+, NE1E2, alkylene-NE1E2, NE1E2E3+Xxe2x88x92, alkylene-NE1E2E3+Xxe2x88x92, ORd, SRd, (CHReCH2O)yRd, (CH2N(E1))yRd, (CH2CH2N(E1))yRd, halogen, trifluoromethyl, nitro, acyl and cyano
where
Rd, E1, E2 and E3 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
Re is hydrogen, methyl or ethyl,
M+ is a cation,
Xxe2x88x92 is an anion and
y is an integer from 1 to 120, or
R1 and R2 and/or R3 and R4 together with the phosphorus atom to which they are bound form a 5- to 8-membered heterocycle which may additionally be fused with one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl groups, where the heterocycle and, if present, the fused-on groups may each bear, independently of one another, one, two, three or four substituents selected from among alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORd, COOxe2x88x92M+, SO3Rd, SOxe2x88x923M+, NE1E2, alkylene-NE1E2, NE1E2E3+Xxe2x88x92, alkylene-NE1E2E3+Xxe2x88x92, ORd, SRd, (CHReCH2O)yRd, (CH2N(E1))yRd, (CH2CH2N(E1))yRd, halogen, trifluoromethyl, nitro, acyl and cyano, where Rd, Re, E1, E2, E3, M+, Xxe2x88x92 und y are as defined above,
R5, R6, R7, R8, R9 and R10 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORf, COOxe2x88x92M+, SO3Rf, SOxe2x88x923M+, NE4E5, NE4E5E6+Xxe2x88x92, alkylene-NE4E5E6+Xxe2x88x92, ORf, SRf, (CHRgCH2O)xRf, (CH2N(E4))xRf, (CH2CH2N(E4))xRf, halogen, trifluoromethyl, nitro, acyl or cyano,
where
Rf, E4, E5 and E6 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
Rg is hydrogen, methyl or ethyl,
M+ is a cation,
Xxe2x88x92 is an anion and
x is an integer from 1 to 120, or
in each case two radicals R5, R6, R7, R8, R9 and R10 bound to adjacent carbon atoms of the benzene rings together with the two adjacent carbon atoms of the benzene ring to which they are bound form a fused ring system having 1, 2 or 3 further rings.
For the purposes of the present invention, the expression xe2x80x9calkylxe2x80x9d encompasses straight-chain and branched alkyl groups. They are preferably straight-chain or branched C1-C12-alkyl groups, more preferably C1-C8-alkyl groups and particularly preferably C1-C4-alkyl groups. Examples of alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl.
Substituted alkyl radicals preferably bear 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from among cycloalkyl, aryl, hetaryl, halogen, NE1E2, NE1E2E3+, carboxyl, carboxylate, xe2x80x94SO3H and sulfonate.
A cycloalkyl group is preferably a C5-C7-cycloalkyl group such as cyclopentyl, cyclohexyl or cycloheptyl.
If the cycloalkyl group is substituted, it preferably bears 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from among alkyl, alkoxy and halogen.
Aryl is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, in particular phenyl or naphthyl.
Substituted aryl radicals preferably bear 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from among alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, xe2x80x94SO3H, sulfonate, NE1E2, alkylene-NE1E2, nitro, cyano and halogen.
Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
Substituted hetaryl radicals preferably bear 1, 2 or 3 substituents selected from among alkyl, alkoxy, carboxyl, carboxylate, xe2x80x94SO3H, sulfonate, NE1E2, alkylene-NE1E2, trifluoromethyl and halogen.
What has been said above in respect of alkyl, cycloalkyl and aryl radicals applies analogously to alkoxy, cycloalkyloxy and aryloxy radicals.
The radicals NE1E2, NE4E5, NE7E8 and NE9E10are preferably N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diisopropylamino, N,N-di-n-butylamino, N,N-di-t-butylamino, N,N-dicyclohexylamino or N,N-diphenylamino.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
For the purposes of the present invention carboxylate and sulfonate are preferably a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic or sulfonic ester function or a carboxamide or sulfonamide function. They include, for example, esters of C1-C4-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
M+ is preferably an alkali metal cation such as Li+, Na+ or K+, NH4+ or a quaternary ammonium compound as is obtainable by protonation or quaternization of amines.
Xxe2x88x92 is preferably halide, particularly preferably Clxe2x88x92 or Brxe2x88x92.
x and y are each, independently of one another, preferably an integer from 2 to 100.
A1 and A2 are each, independently of one another, preferably O, S, SiRaRb, NRc and CR11R12, where Ra, Rb, R11 and R12 are each, independently of one another, hydrogen, C1-C8-alkyl, C5-C8-cycloalkyl, aryl or hetaryl. In particular, Ra, Rb, R11 and R12 are each, independently of one another, hydrogen or C1-C4-alkyl such as methyl, ethyl, n-propyl, n-butyl or tert-butyl. Ra and Rb are particularly preferably both methyl. R11 and R12 are also particularly preferably both methyl.
It is preferred that one of the radicals A1 or A2 is O or S and the other is CR11R12.
It is preferred that one of the radicals A1 or A2 is a single bond and the other is O, S, SiRaRb, NRc or CR11R12.
In a first preferred embodiment, the radicals R1 and R2 or R3 and R4 are not connected by a bridge. In this case, the radicals R1 and R2 and/or R3 and R4 are preferably selected from among substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted hetaryl. The radicals R1, R2, R3 and R4 are each, independently of one another, preferably phenyl radicals which may bear one, two or three substituents selected from among alkyl, alkoxy, halogen, trifluoromethyl, nitro, cyano, alkoxycarbonyl and carboxyl.
In a further preferred embodiment, the radicals R1 and R2 or R3 and R4 are connected by a bridge. In that case, R1 and R2 and/or R3 and R4 together with the phosphorus atom to which they are bound preferably form a five- to eight-membered heterocycle which may additionally be fused with one, two or three cycloalkyl, heterocycloalkyl, aryl or hetaryl groups, where the heterocycle and, if present, the fused-on groups may each bear, independently of one another, one, two, three or four substituents selected from among alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORd, COOxe2x88x92M+, SO3Rd, SOxe2x88x923M+, NE1E2, alkylene-NE1E2, NE1E2E3+Xxe2x88x92, alkylene-NE1E2E3+Xxe2x88x92, ORd, SRd, (CHReCH2O)yRd, (CH2N(E1) )yRd, (CH2CH2N(E1))yRd, halogen, trifluoromethyl, nitro, acyl and cyano, where Rd, Re, E1, E2, E3, M+, Xxe2x88x92 and y are as defined above.
Preference is given to the radicals R1 and R2 and/or R3 and R4 together with the phosphorus atom to which they are bound forming a phosphine radical of the formula II 
where
D together with the phosphorus atom to which it is bound forms a 5- to 8-membered heterocycle which may be fused with one, two or three cycloalkyl, heterocycloalkyl, aryl and/or hetaryl groups, where the fused-on groups may each bear, independently of one another, one, two, three or four substituents selected from among alkyl, alkoxy, halogen, SO3H, sulfonate, NE1E2, alkylene-NE1E2, nitro, cyano, carboxyl and carboxylate, and/or D may bear one, two or three substituents selected from among alkyl, alkoxy, substituted or unsubstituted cycloalkyl and substituted or unsubstituted aryl, and/or D may be interrupted by 1, 2 or 3 substituted or unsubstituted heteroatoms.
The radical D is preferably a C2-C6-alkylene bridge which may be fused with 1 or 2 aryl groups and/or may bear a substituent selected from among alkyl, substituted or unsubstituted cycloalkyl and substituted or unsubstituted aryl and/or may be interrupted by a substituted or unsubstituted heteroatom.
The fused-on aryls of the radicals D are preferably benzene or naphthalene. Fused-on benzene rings are preferably unsubstituted or bear 1, 2 or 3, in particular 1 or 2, substituents selected from among alkyl, alkoxy, halogen, SO3H, sulfonate, NE7E8, alkylene-NE7E8, trifluoromethyl, nitro, carboxyl, alkoxycarbonyl, acyl and cyano. Fused-on naphthalenes are preferably unsubstituted or bear 1, 2 or 3, in particular 1 or 2, of the substituents mentioned above for the fused-on benzene rings on the ring which is not fused on and/or on the fused-on ring. In the case of the substituents on the fused-on aryls, alkyl is preferably C1-C4-alkyl and in particular methyl, isopropyl or tert-butyl. Alkoxy is preferably C1-C4-alkoxy and in particular methoxy. Alkoxycarbonyl is preferably C1-C4-alkoxycarbonyl. Halogen is particularly preferably fluorine or chlorine.
If the C2-C6-alkylene bridge of the radical D is interrupted by 1, 2 or 3 substituted or unsubstituted heteroatoms, these are preferably selected from among O, S, NRi and SiRiRi, where the radicals Ri are each, independently of one another, alkyl, cycloalkyl or aryl. Preference is given to the C2-C6-alkylene bridge of the radical D being interrupted by a substituted or unsubstituted heteroatom.
If the C2-C6-alkylene bridge of the radical D is substituted, it preferably bears 1, 2 or 3 substituents, in particular 1 substituent, selected from among alkyl, cycloalkyl and aryl, where the aryl substituent may bear 1, 2 or 3 of the substituents mentioned for aryl. The alkylene bridge D preferably bears one substituent selected from among methyl, ethyl, isopropyl, phenyl, p-(C1-C4-alkyl)phenyl, preferably p-methylphenyl, p-(C1-C4-alkoxy)phenyl, preferably p-methoxyphenyl, p-halophenyl, preferably p-chlorophenyl, and p-trifluoromethylphenyl.
The radical D is preferably a C3-C6-alkylene bridge which may be fused and/or substituted and/or interrupted by substituted or unsubstituted heteroatoms as described above. In particular, the radical D is a C3-C6-alkylene bridge which is fused with one or two benzene and/or naphthalene groups, where the benzene or naphthalene groups may bear 1, 2 or 3, in particular 1 or 2, of the abovementioned substituents.
Preference is given to the radical D together with the phosphorus atom to which it is bound (i.e. the radicals R1 and R2 or R3 and R4 together with the phosphorus atom to which they are bound) forming a radical selected from among radicals of the formulae II.1 to II.4
where
Z1 is O, S, NRi or SiRiRi, where
Ri is alkyl, cycloalkyl or aryl, or
Z1 is a C1-C3-alkylene bridge which may contain a double bond and/or bear an alkyl, cycloalkyl or aryl substituent, where the aryl substituent may bear one, two or three of the substituents mentioned for aryl, or
Z1 is a C2-C3-alkylene bridge which is interrupted by O, S, NRi or SiRiRi,
R13, R14, R15, R16, R17, R18, R19 R20, R21, R22, R23 and R24 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, SO3H, sulfonate, NE7E8, alkylene-NE7E8, trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, where E7 and E8 are each, independently of one another, hydrogen, alkyl, cycloalkyl or aryl.
D is preferably a radical of the formula II.1 in which R13, R14, R15 and R16 are each hydrogen.
D is preferably a radical of the formula II.2, in which R13 R14, R15 and R16 are each hydrogen.
The radical Z1 in the formulae II.1 and II.4 is preferably O.
The radicals R5, R6, R7, R8, R9 and R10 in the compounds of the formula I are preferably selected from among hydrogen, alkyl, cycloalkyl, aryl and hetaryl. It is preferred that R5, R7, R8 and R10 are each hydrogen and R6 and R9 are each C1-C4-alkyl such as methyl, ethyl, n-propyl, n-butyl or tert-butyl.
Preference is given to at least one of the radicals R5, R6, R7, R8, R9 and R10 being a polar (hydrophilic) group, which then generally results in water-soluble catalysts. The polar groups are preferably selected from among COORf, COOxe2x88x92M+, SO3Rf, SOxe2x88x923M+, NE4E5, alkylene-NE4E5, NE4E5E6+Xxe2x88x92, alkylene-NE4E5E6+Xxe2x88x92, ORf, SRf, (CHRgCH2O)xRf or (CH2CH2N(E4))xRf, where E4, E5, E6, Rf, Rg, M+, Xxe2x88x92 and x are as defined above.
If two radicals selected from among R5, R6, R7R8, R9 and R10 which are bound to adjacent carbon atoms of the benzene rings form a fused-on ring system, this system is preferably a benzene or naphthalene unit. Fused-on benzene rings are preferably unsubstituted or bear 1, 2 or 3, in particular 1 or 2, substituents selected from among alkyl, alkoxy, halogen, SO3H, sulfonate, NE4E5, alkylene-NE4E5, trifluoromethyl, nitro, carboxyl, alkoxycarbonyl, acyl and cyano. Fused-on naphthalenes are preferably unsubstituted or bear 1, 2 or 3, in particular 1 or 2, of the substituents mentioned above for the fused-on benzene rings on the ring which is not fused on and/or on the fused-on ring.
In a preferred embodiment of the process of the present invention, used is made of a hydroformylation catalyst in which the bidentate phosphine ligand of the formula I is selected from among compounds of the formulae I.1 to I.3
where
A1 is a single bond, O, S, SiRaRb, NRc or CR11R12, where Ra, Rb, Rc, R11 and R12 are each, independently of one another, hydrogen or C1-C4-alkyl,
Z2 and Z3 are each, independently of one another, O, S, NRi SiRiRi or CRiRi, where the radicals Ri are each, independently of one another, alkyl, cycloalkyl or aryl, and
R6 and R9 are each, independently of one another, hydrogen or C1-C4-alkyl.
The monodentate phosphine ligand is preferably selected from among trialkylphosphines such as triethylphosphine, tri-n-propyl-phosphine, triisopropylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, dialkylarylphosphines such as diethylphenylphosphine, alkyldiarylphosphines such as diphenylmethylphosphine and diphenylethylphosphine, triarylphosphines such as triphenylphosphine, tri(p-tolyl)-phosphine, tricycloalkylphosphines such as tricyclohexylphosphine and mixtures thereof. Preference is given to using triarylphosphines, in particular triphenylphosphine.
The catalysts used according to the present invention may comprise one or more monodentate phosphine ligands and one or more bidentate phosphine ligands.
In addition to the above-described ligands, at least one further ligand selected from among halides, amines, carboxylates, acetylacetonate, arylsulfonates and alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF3, phospholes, phosphabenzenes and monodentate, bidentate and polydentate phosphinite, phosphonite, phosphoramidite and phosphite ligands may also be present in the catalysts.
The metal of transition group VIII is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium, in particular cobalt, rhodium, ruthenium or iridium.
The compounds of the formula I used according to the present invention can be prepared, for example, starting from a compound of the formula I.a 
where
Ya and Yb are each, independently of one another, halogen, OH, OC(O)CF3 or SO3Me where Me=hydrogen, Li, Na or K, where Ya and/or Yb can also be hydrogen when at least one of the radicals R5 and R10 is hydrogen, an alkoxy group or an alkoxycarbonyl group which is located in the ortho position relative to Ya and/or Yb, and
A1, A2, R5, R6, R7, R8, R9 and R10 are as defined above.
The functionalization of the radicals Ya and Yb to form the radicals PR1R2 and PR3R4 can be carried out by procedures analogous to known methods. For example, it is possible firstly to lithiate compounds of the formula I.a in which Ya and Yb are each halogen, preferably chlorine or bromine, and to react the intermediate formed with a compound bearing a halogen atom, preferably a chlorine atom, on the phosphorus atom, for example a compound of the formula Clxe2x80x94PR1R2 and/or Clxe2x80x94PR3R4.
In place of compounds of the formula I.a in which Ya=Yb=halogen, it is also possible to lithiate compounds I.a in which Ya=Yb=hydrogen and in which hydrogen, an alkoxy group or an alkoxycarbonyl group is located in each of the ortho positions relative to Ya and Yb. Such reactions are described in the literature as xe2x80x9cortho-lithiationxe2x80x9d (cf. for example, D. W. Slocum, J. Org. Chem., 1976, 41, 3652-3654; J. M. Mallan, R. L. Bebb, Chem. Rev., 1969, 693 ff; V. Snieckus, Chem. Rev., 1980, 6, 879-933). The organolithium compounds obtained can then be reacted in the above-described manner with the phosphorus-halogen compounds to form the target compounds I.
In general, the catalysts or catalyst precursors used in each case are converted under hydroformylation conditions into catalytically active species of the formula HxMy(CO)qLIrLIIs, where M is a metal of transition group VIII, LI is a monodentate phosphine ligand, LII is a bidentate phosphine ligand of the formula I and x, y, q, r and s are integers which depend on the valence and type of the metal and on the number of coordination sites occupied by the ligand, with r also being able to be 0. q, r and s are each, independently of one another, preferably a positive integer, e.g. 1, 2 or 3. The sum of q, r and s is preferably from 2 to 5. If desired, the complexes can further comprise at least one of the above-described additional ligands. In the catalyst systems used according to the present invention, it is also not absolutely necessary for a monodentate phosphine ligand complex to be present in the catalytically active species, as long as the catalyst system used comprises at least one such ligand.
In a preferred embodiment, the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction. However, if desired, the catlysts used according to the present invention can also be prepared separately and isolated by customary methods. For the in situ preparation of the catalysts used according to the present invention, it is possible, for example, to react at least one monodentate phosphine ligand, at least one compound of the formula I, a compound or a complex of a metal of transition group VIII, if desired at least one additional ligand and, if desired, an activating agent in an inert solvent under the hydroformylation conditions.
Suitable rhodium compounds or complexes are, for example, rhodium(II) and rhodium(III) salts such as rhodium(III) chloride, rhodium(III) nitrate, rhodium(III) sulfate, potassium-rhodium sulfate, rhodium(II) and rhodium(III) carboxylates, rhodium(II) and rhodium(III) acetate, rhodium(III) oxide, salts of rhodic(III) acid, trisammonium hexachlororhodate(III), etc. Rhodium complexes such as dicarbonylrhodium acetylacetonate, acetylacetonatobisethylenerhodium(I), rhodiumethylhexanoate, etc., are also suitable. Preference is given to using dicarbonylrhodium acetylacetonate or rhodium acetate.
Ruthenium salts or compounds can likewise be used. Suitable ruthenium salts are, for example, ruthenium(III) chloride, ruthenium(IV), ruthenium(VI) and ruthenium(VIII) oxides, alkali metal salts of ruthenium oxo acids, e.g. K2RuO4 or KRuO4, or complexes such as RuHCl(CO)(PPh3)3. It is also possible to use carbonyls of ruthenium, e.g. dodecacarbonyltriruthenium or octadecacarbonylhexaruthenium, or mixed forms in which CO is partly replaced by ligands of the formula PR3, e.g. Ru(CO)3(PPh3)2, in the process of the present invention.
Suitable cobalt compounds are, for example, cobalt(II) chloride, cobalt(II) sulfate, cobalt(II) carbonate, cobalt(II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and also the cobalt-caprolactamate complex. Here too, carbonyl complexes of cobalt, e.g. octacarbonyldicobalt, dodecacarbonyltetracobalt and hexadecacarbonylhexacobalt, can be used.
The abovementioned and further suitable compounds of cobalt, rhodium, ruthenium and iridium are known in principle and are adequately described in the literature or they can be prepared by a person skilled in the art using methods analogous to those for the known compounds.
Suitable activating agents are, for example, Brxc3x6nsted acids, Lewis acids, e.g. BF3, AlCl3, ZnCl2, and Lewis bases.
As solvents, preference is given to using the aldehydes which are formed in the hydroformylation of the respective olefins and also their higher-boiling downstream reaction products, e.g. the products of aldol condensation. Further solvents which can likewise be used are aromatics such as toluene and xylenes, hydrocarbons and mixtures of hydrocarbons; these can also be used for dilution of the above-mentioned aldehydes and the downstream products of the aldehydes. Further suitable solvents are esters of aliphatic carboxylic acids with alkanols, for example, ethyl acetate or Texanol(trademark), ethers such as tert-butyl methyl ether and tetrahydrofuran. In the case of sufficiently hydrophilic ligands, it is also possible to use alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone, etc. Furthermore, xe2x80x9cionic liquidsxe2x80x9d can also be used as solvents. These are liquid salts, for example N,Nxe2x80x2-dialkylimidazolium salts such as N-butyl-Nxe2x80x2-methylimidazolium salts, tetraalkylammonium salts such as tetra-n-butylammonium salts, N-alkylpyridinium salts such as N-butylpyridinium salts, tetraalkylphosphonium salts such as trishexyl(tetradecyl)phosphonium salts, e.g. the tetrafluoro-borates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
It is also possible to carry out the reactions in water or aqueous solvent systems comprising water together with a water-miscible solvent, for example an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a ketone such as acetone or methyl ethyl ketone or another solvent. For this purpose, preference is given to using ligands of the formula I which are modified with polar groups, for example ionic groups such as SO3Me, CO2Me where Me=Na, K or NH4 or N(CH3)3+. The reactions then occur as a two-phase catalysis in which the catalyst is present in the aqueous phase and starting materials and products form the organic phase. The reaction in the xe2x80x9cionic liquidsxe2x80x9d can also be carried out as a two-phase catalysis.
The molar ratio of phosphorus-containing ligands to metal of transition group VIII is generally in a range from about 1:1 to 1 000:1.
Substrates which can be used in the hydroformylation process of the present invention are in principle all compounds which contain one or more ethylenically unsaturated double bonds. They include, for example, olefins such as xcex1-olefins, internal straight-chain and internal branched olefins. Suitable xcex1-olefins are, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, etc.
Preferred branched, internal olefins are C4-C20-olefins such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched, internal octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
Further olefins suitable for the hydroformylation process are C5-C8-cycloalkenes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and derivatives thereof, e.g. their C1-C20-alkyl derivatives having from 1 to 5 alkyl substituents. In addition, vinylaromatics such as styrene, xcex1-methylstyrene, 4-isobutylstyrene, etc., can also be hydroformylated. Further suitable olefins for the hydroformylation reaction are xcex1,xcex2-ethylenically unsaturated monocarboxylic and/or dicarboxylic acids, their esters, monoesters and amides, e.g. acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl 3-pentenoate, methyl 4-pentenoate, methyl oleate, methyl acrylate, methyl methacrylate, unsaturated nitriles such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., C1-C20-alkenols, -alkenediols and -alkadienols, e.g. 2,7-octadien-1-ol. Further suitable substrates are dienes or polyenes having isolated or conjugated double bonds. These include, for example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and also homopolymers and copolymers of butadiene.
The unsaturated compound used for the hydroformylation is preferably selected from among internal linear olefins and olefin mixtures in which at least one internal linear olefin is present. Preferred linear (straight-chain) internal olefins are C4-C20-olefins such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, etc. and mixtures thereof.
The hydroformylation process of the present invention is preferably carried out using an industrially available olefin mixture which comprises, in particular, at least one internal linear olefin. Such mixtures include, for example, the Ziegler olefins obtained by targeted ethene oligomerization in the presence of alkylaluminum catalysts. These are essentially unbranched olefins having a terminal double bond and an even number of carbon atoms. Suitable olefin mixtures also include the olefins obtained by ethene oligomerization in the presence of various catalyst systems, e.g. the predominantly linear xcex1-olefins obtained in the presence of alkylaluminum chloride/titanium tetrachloride catalysts and the xcex1-olefins obtained in the presence of nickel-phosphine complexes as catalysts by means of the Shell Higher Olefin Process (SHOP). Suitable industrially available olefin mixtures are also obtained in the dehydrogenation of appropriate petroleum fractions, e.g. kerosene or diesel oil fractions. The conversion of paraffins, predominantly n-paraffins, into olefins is carried out using essentially three methods:
thermal cracking (steam cracking),
catalytic dehydrogenation and
chemical dehydrogenation by chlorination and dehydrochlorination.
Thermal cracking leads predominantly to xcex1-olefins, while the other variants produce olefin mixtures which generally have relatively large proportions of olefins containing an internal double bond. Suitable olefin mixtures also include the olefins obtained in metathesis or telomerization reactions. They include, for example, the olefins from the Phillips triolefin process, a modified SHOP process, comprising ethylene oligomerization, double bond isomerization and subsequent metathesis (ethenolysis).
Further industrial olefin mixtures which can be used in the hydroformylation process of the present invention are selected from among dibutenes, tributenes, tetrabutenes, dipropenes, tripropenes, tetrapropenes, mixtures of butene isomers, in particular raffinate II, dihexenes, dimers and oligomers from the Dimersol(copyright) process of IFP, the Octol(copyright) process of Hxc3xcls, the Polygas process, etc.
Preference is given to using 1-butene-containing hydrocarbon mixtures. These include, in particular, raffinate II. Suitable 1-butene-containing hydrocarbon mixtures may contain a proportion of saturated hydrocarbons. Mixtures having a low proportion of high-boiling components are advantageous.
The hydroformylation reaction in the process of the present invention can be carried out continuously, semicontinuously or batchwise. The advantages of the process of the present invention are especially evident when the process is carried out semicontinuously or, in particular, continuously. The invention provides a process which comprises
(i) reacting the compound(s) containing at least one ethylenically unsaturated double bond in a reaction zone in the presence of carbon monoxide, hydrogen and the catalyst system,
(ii) taking an output from the reaction zone and separating it into a fraction enriched in product and a fraction enriched in catalyst system,
(iii) if desired, subjecting the fraction enriched in catalyst system obtained in step (ii) to work-up and
(iv) returning at least part of the fraction enriched in catalyst system, if desired after work-up, to the reaction zone,
where at least one of these steps (ii) to (iv) is carried out essentially in the absence of carbon monoxide and hydrogen and in the presence of at least one monodentate phosphine ligand.
In a first preferred embodiment, the steps (i) to (iv) are all carried out in the presence of at least one monodentate phosphine ligand.
In a second preferred embodiment, only some of the steps (i) to (iv) are carried out in the presence of a monodentate phosphine ligand. According to the present invention, the presence of monodentate phosphine ligands in reaction steps carried out in the absence of carbon monoxide and hydrogen is absolutely necessary.
Step (i)
Reactors suitable for a continuous reaction are known to those skilled in the art and are described, for example, in Ullmanns Enzyklopxc3xa4die der technischen Chemie, vol. 1, 3rd edition, 1951, p. 743 ff.
Suitable pressure-rated reactors are likewise known to those skilled in the art and are described, for example, in Ullmanns Enzyklopxc3xa4die der technischen Chemie, vol. 1, 3rd edition, 1951, p. 769 ff. In general, the process of the present invention is carried out using an autoclave which may, if desired, be provided with a stirrer and an internal lining.
The composition of the synthesis gas comprising carbon monoxide and hydrogen used in step (i) of the process of the present invention can vary within a wide range. The molar ratio of carbon monoxide to hydrogen is generally from about 5:95 to 70:30, preferably from about 40:60 to 60:40. Particular preference is given to using a molar ratio of carbon monoxide to hydrogen in the region of 1:1.
The temperature in the hydroformylation reaction is generally in a range from about 20 to 180xc2x0 C., preferably from about 50 to 150xc2x0 C. The reaction is generally carried out at the partial pressure of the reaction gas at the reaction temperature selected. In general, the pressure is in a range from about 1 to 700 bar, preferably from 1 to 600 bar, in particular from 1 to 300 bar. The reaction pressure can be varied as a function of the activity of the hydroformylation catalyst used in the process of the present invention. In general, the catalysts used according to the present invention permit a reaction in a low pressure range, for instance in the range from 0.1 to 100 bar.
Step (ii)
The separation of the output taken from the reaction zone into a fraction enriched in product and a fraction enriched in catalyst system is carried out by customary methods known to those skilled in the art. Preference is given to distillation using known separation apparatuses such as distillation columns, e.g. tray columns which may, if desired, be equipped with bubble caps, sieve plates, sieve trays, valves, etc., and evaporators, e.g. thin film evaporators, falling film evaporators, wiped film evaporators, etc.
In a useful embodiment of the process of the present invention, step (i) is carried out in the absence of a monodentate phosphine ligand and step (ii) is carried out in the presence of at least one monodentate phosphine ligand. The monodentate phosphine ligand can, for example, be added to the output from the reaction zone.
Step (iii)
The fraction enriched in catalyst system can be subjected to one or more work-up steps before it is returned to the hydroformylation process. Such steps include, for example, purification steps for the partial or complete removal of high-boiling products of the hydroformylation reaction. Suitable purification processes are, for example, membrane filtration, isolation of the catalyst, e.g. by precipitation of a catalyst-cocatalyst complex, injection of steam to achieve partial or complete removal of high-boiling by-products, etc.
Step (iv)
All or some of the fraction enriched in catalyst system is, if desired after work-up as described above, fed into the reaction zone and thus returned to the hydroformylation process. If the hydroformylation stage comprises more than one reactor, all or some of the fraction enriched in catalyst system can be fed into each of the reactors. If desired, the monodentate phosphine ligand can be separated off by customary methods known to those skilled in the art before the fraction enriched in catalyst system is returned to the reaction zone.
It is advantageous for the catalyst systems used according to the present invention and the catalytically active species formed therefrom under the hydroformylation conditions to be stable in the absence of CO and H2 (synthesis gas), too. The disadvantages observed according to the prior art in the case of hydroformylation catalysts based on bidentate phosphine ligands and especially those having a xanthene skeleton, for example irreversible decomposition or a pronounced tendency to crystallize in the absence of CO and H2, generally do not occur. The catalysts used according to the present invention thus have long catalyst operating lives and are also suitable for continuous hydroformylation processes. The latter can advantageously comprise one or more process steps such as the separation of reaction products and the work-up of catalyst-containing fractions which are carried out in the absence of CO and H2.
Surprisingly, the catalysts used according to the present invention generally display a selectivity which is as good as or better than corresponding catalysts from the prior art which contain no monodentate phosphine ligand. Thus, the catalyst systems used according to the present invention advantageously display a high selectivity to xcex1-aldehydes or xcex1-alcohols in the hydroformylation of xcex1-olefins. In general, good yields of n-aldehydes or n-alcohols are generally also obtained. Surprisingly, it is generally also possible to stabilize higher rhodium concentrations by use of a monodentate phosphine ligand in the catalyst systems than is the case for catalysts from the prior art.
Catalysts of the above-described type which comprise chiral compounds of the formula I are suitable for enantioselective hydroformylation.
The above-described catalysts can also be immobilized on a suitable support, e.g. glass, silica gel, synthetic resins, etc., by suitable methods, e.g. by bonding via functional groups suitable as anchor groups, adsorption, grafting, etc. They are then also suitable for use as solid phase catalysts.
The invention is illustrated by the nonrestrictive examples below.